Organometallic compound preparation

ABSTRACT

An apparatus for continuously manufacturing organometallic compounds is provided where the apparatus has a source of a first reactant stream wherein the first reactant comprises a metal; a source of a second reactant stream; a laminar flow contacting zone for cocurrently contacting the first reactant stream and the second reactant stream; a mixing zone comprising a turbulence-promoting device; and a heat transfer zone.

This application is a divisional application of U.S. Ser. No.13/586,751, filed on Aug. 15, 2012, which claims the benefit of priorityunder 35 U.S.C. §119(e) to U.S. Provisional Application No. 61/523,582,filed Aug. 15, 2011, the entire contents of which application areincorporated herein by reference.

The present invention relates to the field of metal-containing compoundsand particularly to the field of preparing organometallic compounds.

Metal-containing compounds are used in a variety of applications, suchas catalysts and sources for growing metal films. One use of suchcompounds is in the manufacture of electronic devices such assemiconductors. Many semi-conducting materials are manufactured usingwell-established deposition technologies that employ ultrapuremetalorganic (organometallic) compounds, for example, metalorganic vaporphase epitaxy, metalorganic molecular beam epitaxy, metalorganicchemical vapor deposition and atomic layer deposition.

Many of these organometallic compounds or their starting materials posesignificant challenges in handling, due to their reactivity with air,pyrophoricity and/or toxicity. Care must be taken in the manufacture ofthese organometallic compounds. Conventional organometallic compoundmanufacturing methods are small-scale batch processes where it isrelatively easy to control the reaction and exclude oxygen. The productyields from these batch processes vary across a wide range. For example,conventional batch-processes for manufacturing trimethylgallium,triethylgallium, and trimethylindium have yields of 80-100% beforepurification. Although these processes are effective, they allow onlyfor limited production of the desired compounds. The need for largeramounts of these organometallic compounds means that many suchsmall-scale production runs must be performed, which greatly increasesthe cost of the desired compounds.

U.S. Pat. No. 6,495,707 discloses a method of continuously manufacturingtrimethylgallium (“TMG”) by adding both gallium trichloride andtrimethylaluminum to a reaction center in a distillation column,vaporizing the TMG produced and collecting the TMG from the top of thedistillation column. The figure in this patent shows the reactantsentering the column from opposing inlets. The apparatus in this patentappears to be designed to give turbulent flow for rapid mixing of thereactants. Turbulent flow is defined as having a Reynolds number (“Re”)of ≧4000. However, the yields of TMG obtained from this process are low,only 50-68%, and the purity of the obtained TMG is not discussed.

Chinese published patent application CN 1872861 A discloses animprovement to the process of U.S. Pat. No. 6,495,707 in which anitrogen gas stream is introduced into the bottom of the distillationcolumn to increase agitation in the liquid phase portion in the columnand to promote the generation of TMG, purporting to improve the reactionefficiency. However, the reported yields of TMG in this patentapplication are still low, only 52%, and are no different from thosereported in U.S. Pat. No. 6,495,707.

There remains a need for a method of continuously preparingorganometallic compounds in high yield.

The present invention provides a method of continuously preparing anorganometallic compound comprising: (a) providing an apparatuscomprising a reactor unit, the reactor unit comprising a laminar flowcontacting zone, a mixing zone comprising a turbulence-promoting device,and a heat transfer zone; (b) continuously delivering a first reactantstream and a second reactant stream to the contacting zone to form areaction mixture stream, wherein the first reactant stream and thesecond reactant stream are cocurrent and have substantially laminarflows, and wherein the first reactant is a metal-containing compound;(c) conveying the reaction mixture stream from the contacting zone to aheat transfer zone, and then to the mixing zone; (d) causing thereaction mixture stream to form an organometallic compound productstream; (e) controlling the temperature and pressure of the productstream in the heat transfer zone so as to maintain a majority of theorganometallic compound in a liquid phase; and (f) conveying the productstream to a separation unit to isolate the organometallic compound.

Also provided by the present invention is an apparatus for continuouslymanufacturing an organometallic compound comprising: (a) a source of afirst reactant stream wherein the first reactant comprises a metal; (b)a source of a second reactant stream; (c) a laminar flow contacting zonefor cocurrently contacting the first reactant stream and the secondreactant stream; (d) a mixing zone comprising a turbulence-promotingdevice; and (e) a heat transfer zone.

FIGS. 1-3 are schematic depictions of apparatuses of the inventionsuitable for use with the process of the invention.

FIGS. 4A-4F are schematic cross-sectional depictions of suitablecontacting zone inlets for use in an apparatus suitable for the processof the invention.

FIGS. 5A-5C are cross-sectional schematic depictions of an apparatussuitable for use with the process of the invention.

FIGS. 6A-6C are schematic depictions of an apparatus suitable for usewith the present invention having a plurality of mixing zones.

The articles “a” and “an” refer to the singular and the plural. “Alkyl”includes straight chain, branched and cyclic alkyl. “Halogen” refers tofluorine, chlorine, bromine and iodine. The term “plurality” refers totwo or more of an item. “Stream” refers to the flow of a fluid. “Fluid”refers to a gas, a liquid, or a combination thereof. The term“cocurrent” refers to the flow of two fluids in the same direction. Theterm “countercurrent” refers to the flow of two fluids in opposingdirections. The following abbreviations shall have the followingmeanings: ppm=parts per million; m=meters; mm=millimeters;cm=centimeters; kg=kilograms; kPa=kilopascals; psi=pounds per squareinch; and ° C.=degrees Celsius. In the figures, like numerals refer tolike elements.

It will be understood that when an element is referred to as being “on”another element, it can be directly on the other element or interveningelements may be present therebetween. In contrast, when an element isreferred to as being “directly on” another element, there are nointervening elements present.

It will be understood that, although the terms first, second, third,etc. may be used herein to describe various elements, components,regions, layers, zones or sections, these elements, components, regions,layers, zones or sections should not be limited by these terms. Theseterms are only used to distinguish one element, component, region,layer, zone or section from another element, component, region, layer,zone or section. Thus, a first element, component, region, layer, zoneor section discussed below could be termed a second element, component,region, layer, zone or section without departing from the teachings ofthe present invention.

Furthermore, relative terms, such as “lower” or “bottom” and “upper” or“top,” may be used herein to describe one element's relationship toanother element as may be illustrated in the Figures. It will beunderstood that relative terms are intended to encompass differentorientations of the device in addition to the orientation depicted inthe Figures. For example, if the device in one of the Figures is turnedover, elements described as being on the “lower” side of other elementswould then be oriented on “upper” sides of the other elements. Theexemplary term “lower,” can therefore, encompasses both an orientationof “lower” and “upper,” depending on the particular orientation of thefigure. Similarly, if the device in one of the figures is turned over,elements described as “below” or “beneath” other elements would then beoriented “above” the other elements. The exemplary terms “below” or“beneath” can, therefore, encompass both an orientation of above andbelow.

Unless otherwise noted, all amounts are percentages by weight and allratios are molar ratios. All numerical ranges are inclusive andcombinable in any order except where it is clear that such numericalranges are constrained to add up to 100%.

The present invention provides a method for the continuous preparationof organometallic compounds. An apparatus comprising one or more reactorunits may be used, where each reactor unit comprises: (a) a source of afirst reactant stream wherein the first reactant comprises a metal; (b)a source of a second reactant stream; (c) a laminar flow contacting zonefor cocurrently contacting the first reactant stream and the secondreactant stream; (d) a mixing zone comprising a turbulence-promotingdevice; and (e) a heat transfer zone. Suitable reactors may include aplurality of mixing zones and/or a plurality of heat transfer zones. Inthis method, a first reactant stream is continuously delivered to thecontacting zone of the reactor unit, and a second reactant stream iscontinuously delivered to the contacting zone to form a reaction mixturestream. The flows of the first reactant stream and the second reactantstream are cocurrent and substantially laminar. At least the firstreactant is a metal-containing compound. The second reactant mayoptionally be a metal-containing compound, depending upon the particularreactants used and the organometallic compound desired. The reactionmixture stream is subjected to conditions to form an organometallicproduct stream and the temperature and pressure of the product streamare controlled in the heat transfer zone so as to maintain a majority ofthe organometallic compound in a liquid phase. The organometallicproduct stream is then conveyed from the reactor unit to a separationunit to isolate the organometallic compound.

A variety of different reactor units may be used in the present process.FIG. 1 is a schematic diagram of an apparatus suitable for use with theprocess of the invention having reactor 10 having a contacting zone 15,a mixing zone 20, and a heat transfer zone 45. Each of contacting zone15, mixing zone 20, and heat transfer zone 45 may be any suitablelength. In FIG. 1, contacting zone 15 and heat transfer zone 45 areshown to be co-extensive, but that is not required. Reactor 10 has afirst inlet 25 and a second inlet 30 for feeding the first and secondreactant streams, respectively, into contacting zone 15. Reactor 10 hasan outlet 35 which is in fluid communication with separation unit 40.

Referring to FIG. 1, in operation, the first reactant stream 17 isconveyed into contacting zone 15 of reactor 10 by way of first inlet 25.The second reactant stream 27 is conveyed into contacting zone 15 ofreactor 10 by way of second inlet 30. The flows of the first reactantstream and the second reactant stream in the contacting zone arecocurrent and laminar. The resultant reaction mixture stream is conveyedalong reactor 10 and into mixing zone 20, which is designed to promoteturbulence. The organometallic compound product stream exits reactor 10by way of outlet 35 and is then conveyed to separation unit 40 where thedesired organometallic compound is separated from by-products, unreactedfirst and second reactants, and the like.

FIG. 2 shows an alternate reactor similar to that shown in FIG. 1,except that reactor 10 also includes a reaction zone 50 following mixingzone 20. Reactor 10 also has a plurality of heat transfer zones 45, withone heat transfer zone 45 a being coextensive with contacting zone 15,and a second heat transfer zone 45 b being co-extensive with reactionzone 50. It will be appreciated by those skilled in the art that mixingzone 20 may also be contained within a heat transfer zone, not shown,and that the heat transfer zones need not be co-extensive with either ofthe contacting zone or the reaction zone.

FIG. 3 illustrates a yet another suitable reactor 10 having contactingzone 15, mixing zone 20, and reaction zone 50. Each of the contactingzone, mixing zone and reaction zone may be contained within one or moreheat transfer zones, not shown in FIG. 3. Mixing zone 20 is illustratedas a “U-bend” (180°), but other suitable bend configurations including45°, 90°, and 360° bends, not shown, may be used.

Referring to FIG. 1, first reactant stream 17 and second reactant stream27 are delivered to contacting zone 15 with laminar flows. FIGS. 4A-4Fare schematic cross-sectional views of alternate contacting zone 15 ofreactor 10. FIG. 4A illustrates contacting zone 15 in rector 10 having asingle first inlet 25 and a single second inlet 30, the second inletbeing located in the relative center of the end of reactor 10. FIG. 4Billustrates contacting zone 15 similar to that in FIG. 4A, except that abaffle plate 11 is present to delay the onset of contact of firstreactant stream 17 and second reactant stream 27. An alternatecontacting zone 15 is shown in FIG. 4C having a plurality of firstinlets 25 (only 2 are shown) and a single second inlet 30. FIG. 4Dillustrates a further alternative of contacting zone 15 where secondinlet 30 extends into reactor 10. In FIG. 4E, another alternativecontacting zone 15 is illustrated having a plurality of first inlets 25(only 2 are shown) and having second inlet 30 extending into reactor 10.FIG. 4F illustrates an alternate contacting section similar to thatshown in FIG. 4D. The plurality of first inlets 25 in FIGS. 4C and 4Emay be arranged in any pattern around second inlet 30.

Reactor 10 may be composed of any suitable material which will not reactwith the reactants used or the organometallic compound to be produced.Suitable materials include, without limitation: glass such asborosilicate glass and PYREX glass; plastics including perfluorinatedplastics such as poly(tetrfluoroethylene); quartz; or metal. Metals arepreferred, and include, without limitation, nickel alloys and stainlesssteels. Suitable stainless steels include, but are not limited to, 304,304 L, 316, 316 L, 321, 347 and 430. Suitable nickel alloys include, butare not limited to, INCONEL, MONEL, and HASTELLOY corrosion-resistantalloys. Optionally, when reactor 10 is composed of a metal, such reactormay be coated with a suitable coating, such as silicon nitride orsilicon tetrafluoride, to improve corrosion resistance. Such coatingsmay be applied by any suitable technique, such as by vapor deposition.The reactor may be composed of a mixture of materials, such asglass-lined stainless steel. The choice of suitable material for thereactor is well within the ability of those skilled in the art. Suitablereactors are generally commercially available from a variety of sources.

The dimensions of reactor 10 are not critical. Reactor 10 may have anysuitable length and diameter. The choice of such length and diameterwill depend on the volume of the organometallic compound to be produced,and the amount of reaction time needed between the reactants, amongother factors within the ability of those skilled in the art. Typicallengths range from 1 to 15 m, preferably from 1.5 to 12 m, morepreferably from 1.5 to 10 m, and even more preferably from 1.5 to 8 m.Particularly preferred lengths are 1.5, 2, 3, 4, 5, 6, 7, 8, and 10 m.Typical diameters range from 5 mm to 25 cm, more preferably from 5 mm to20 cm, still more preferably from 5 mm to 15 cm, yet more preferablyfrom 5 mm to 5 cm, even more preferably from 6 to 25 mm, and mostpreferably from 8 to 10 mm. Particularly preferred diameters are 5, 6,7, 8, 9, 10, 12, and 15 mm.

Reactor 10 includes a contacting zone, at least one mixing zone and oneor more heat transfer zones. The contacting zone typically extends intothe heat transfer zone. Preferably, the contacting zone is containedwithin a heat transfer zone. More preferably, the contacting zone isco-extensive with a heat transfer zone, or a plurality of heat transferzones. The length of the contacting zone will depend on the reactantsused and the organometallic compound to be produced, whether thereaction is exothermic or endothermic, the efficiency of the mixingsection, the velocities of the reactants, and the time needed for thereaction, among other factors within the ability of one skilled in theart. As an example, the contacting zone may comprise from 1 to 99% ofthe reactor length, preferably from 1 to 95%, more preferably from 1 to75%, and yet more preferably from 5 to 50%. As the first and secondreactant streams in the contacting zone have laminar flow, little mixingoccurs in the contacting zone. Instead, reaction between the reactantsoccurs at the interface of the two streams. In this way, the initialrate of reaction can a controlled.

The present reactor contains one or more mixing zones designed topromote turbulence. That is, the mixing zone is designed to promote aflow of the reactant streams that is more turbulent than the laminarflow of the reactants in the contacting zone. The mixing zone may haveany suitable design that can be used to control the level of mixing ofthe reactants. Exemplary mixing zones may include static mixers,venturis, orifices, bends, wavy-walled reactors, and any other suitablemixing means. Preferably, the mixing zone comprises a mixing meanschosen from venturis, orifices, bends, wavy-walled reactors andcombinations thereof, and more preferably venturis, bends, wavy-walledreactors and combinations thereof. A variety of “bends” may be used asmixing means, such as elbows (having a bend angle of 1-90°), U-bends(having a bend angle of 91-180°), and loops (having a bend angle of181-360°). Combinations of bends may be employed, such as in a“serpentine” mixing zone, as shown in FIG. 6C. The bends may have anysuitable radius of curvature, such as from 0.5 cm to 1 m, preferablyfrom 1 cm to 50 cm, more preferably from 1 cm to 30 cm, and mostpreferably from 1 to 10 cm. Particularly preferred radii of curvatureare 3, 3.2, 3.25, 3.3, 3.5, 3.6, 3.7, 3.8, 4, 4.1, 4.25, 4.5, 4.6, 4.75,5, 5.1, 5.2, 5.25, 5.5, 5.6, 5.7, 6, 6.1, 6.2, 6.25, 6.3, 6.35, 6.4,6.5, 7, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 76.75, 8, 8.1, 8.25, 8.4, 8.5,8.6, 8.7, 8.8, 8.9, 9, 9.25, 9.5, 9.75, and 10 cm. The smaller theradius of curvature, the more secondary mixing is promoted.

The choice of the particular mixing means will depend on how exothermicthe reaction is. For example, for relatively more exothermic reactions,it is preferred that the mixing zone comprise a mixing means thatprovides a relatively lesser degree of mixing, such as venturis, bends,wavy-walled reactors, and combinations thereof. It is preferred that themixing means used for relatively more exothermic reactions providesmicro flow regimes rather than complete turbulence. For relatively lessexothermic reactions and for endothermic reactions, a mixing zonecomprising any suitable mixing means to promote the desired level ofmixing may be used. The size of the mixing means may be easily selectedby one skilled in the art so as to provide the desired level of mixing.Such mixing zones may be placed at any suitable point along the reactor.One or more mixing zones may be used in the present reactor. Each mixingzone may include one or more mixing means. When more than one mixingmeans, such as when more than one mixing zone having a single mixingmeans or when a single mixing zone having a plurality of mixing means,is used, such mixing means may be the same or different. As used herein,“different mixing means” includes two or more of the same type of mixingmeans having different sized components, such as two or more venturishaving different diameter openings or two or more bends having differentradii of curvature. When two or more wavy-walled reactors are used, eachsuch reactor may have different lengths and different radii of theelements composing the wavy-walled section. Preferably, a plurality ofmixing means are used. When the present reactor is used to continuouslymanufacture an organometallic compound through a relatively moreexothermic reaction, it is preferred that a plurality of mixing zonesare used. It is further preferred that such plurality of mixing zones becomposed of different mixing means.

FIG. 3, discussed above, illustrates a U-bend as mixing zone 20. FIG. 5Aillustrates a cross-sectional view of reactor 10 having contacting zone15, mixing zone 20, and heat transfer zone 45 containing both contactingzone 15 and mixing zone 20, where mixing zone 20 is composed of awavy-walled reactor having elements 21. FIG. 5B illustrates across-sectional view of reactor 10 having mixing zone 20 composed of aventure having elements 21 a. In FIG. 5B, both contacting zone 15 andmixing zone 20 are contained within heat transfer zone 45. FIG. 5C showsa cross-sectional view of reactor 10 having mixing zone 20 composed of aplurality of venturis, 21 a and 21 b. A plurality of mixing zones, 20 aand 20 b, separated by reaction zone 50 is shown in FIG. 6A, where eachmixing zone is a U-bend and each U-bend has a different radius ofcurvature, not shown. FIG. 6B illustrates a reactor 10 having aplurality of mixing zones, 20 a and 20 b, and reaction zone 50 disposedwithin heat transfer zone 45. Both contacting zone 15 and mixing zone 20a are contained within a heat transfer zone, not shown. FIG. 6Cillustrates reactor 10 having contacting zone 15, a plurality of mixingzones 20 a, 20 b, and 20 c, and reaction zone 50. In FIG. 6C, theplurality of mixing zones are shown connected in series (a “serpentine”mixing zone), with each of 20 a, 20 b, and 20 c having a differentradius of curvature (not shown). Heat transfer zones are not shown inFIGS. 5C, 6A and 6C.

The present reaction may optionally contain a reaction zone following amixing zone. Preferably, the present reactor does contain at least onereaction zone. When a plurality of mixing zones are used, a reactionzone may be present after any of the mixing zones, and preferably aftereach mixing zone. The length of the reaction zone will depend on thereactants used and the organometallic compound to be produced, whetherthe reaction is exothermic or endothermic, the efficiency of the mixingsection, the rate of the reaction, and the time needed for the reaction,among other factors within the ability of one skilled in the art. As anexample, the reaction zone may comprise from 1 to 99% of the reactorlength, preferably from 1 to 95%, more preferably from 1 to 75%, and yetmore preferably from 5 to 50%. The contacting zone and any reaction zonemay be have the same length or different lengths.

The present reactor also has at least one heat transfer zone. Such heattransfer zone may include any or all of the contacting zone, the mixingzone and the optional reaction zone. Preferably, the heat transfer zoneincludes the contacting zone and any reaction zone. For example, when areactor includes both a contacting zone and a reaction zone, each ofsuch zones may be contained within a single heat transfer zone or eachmay be contained in a separate heat transfer zone. The contacting zonemay be composed of one or more heat transfer zones, and preferably oneheat transfer zone. Preferably, the contacting zone is co-extensive witha heat transfer zone. It is also preferred that any reaction zone becontained within a heat transfer zone, and more preferably that eachreaction zone be co-extensive with a heat transfer zone.

Suitable heat transfer zones include heat exchanges such as condensers,chillers, and heaters. The selection of a specific heat transfer zone,its length and its location in the reactor, will depend on the size ofthe reactor, the volume of organometallic compound to be produced,whether the reaction to produce the organometallic compound isexothermic or endothermic, and the particular organometallic compound tobe produced, among other factors known to those skilled in the art. Suchselection of the heat transfer zone and its location in the reactor iswithin the ability of one skilled in the art.

The first reactant stream enters the contacting zone of the reactorthrough the first inlet. The first reactant may be in the liquid-phase,the vapor phase or in both liquid- and vapor-phases. Preferably, amajority of the first reactant is in the liquid-phase. The secondreactant stream enters the contacting zone of the reactor through thesecond inlet. The second reactant may be in the liquid-phase, the vaporphase or in both liquid- and vapor-phases. Preferably, a majority of thesecond reactant is in the liquid-phase. It is also preferred that thefirst reactant and the second reactant are both in the liquid-phase, thevapor-phase, or in both liquid- and vapor-phases. It is furtherpreferred that both first reactant and second reactant are in theliquid-phase.

Relatively low-melting point solid reactants may be used in the presentprocess by appropriately heating the reactor to a temperature above themelting point of the reactant. Reactants that are either solid or liquidat the temperature of the reactor may be dissolved in a solvent toprovide a liquid-phase reactant that is then conveyed into the reactor.An organic solvent is preferred when a reactant or the organometalliccompound produced is a solid at the temperature of the reactor. Anyorganic solvent may be used provided that it does not react with ordestabilize the reactants or the organometallic compound produced.Suitable solvents are known to those skilled in the art. Preferredsolvents are hydrocarbons such as linear alkyl benzenes, toluene,xylene, mesitylene, durene, quinoline, isoquinoline, squalane, indane,1,2,3,4-tetrahydronaphthalene (tetralin), and decahydronaphthalene; andionic liquids. Ionic liquids are generally salts that are liquid at lowtemperatures, having melting points under 100° C. Ionic liquids arecomposed entirely of ions and typically they are composed of bulkyorganic cations and inorganic anions. Due to the high Coulumbic forcesin these compounds, ionic liquids have practically no vapor pressure.Any suitable ionic liquid may be employed as the solvent in the presentinvention. Exemplary cations used in ionic liquids include, but are notlimited to, hydrocarbylammonium cation, hydrocarbylphosphonium cation,hydrocarbylpyridinium cation, and dihydrocarbylimidazolium cation.Exemplary anions useful in the present ionic liquids include, withoutlimitation: chlorometalate anion; fluoroborate anion such astetrafluoroborate anion and hydrocarbyl substituted fluoroborate anion;and fluorophosphate anion such as hexafluorophosphate anion andhydrocarbyl substituted fluorophosphate anion. Exemplary chlorometalateanions include: chloroaluminate anion such as tetrachloroaluminate anionand chlorotrialkylaluminate anion; chlorogallate anions such aschlorotrimethylgallate; and tetrachlorogallate, chloroindate anions suchas tetrachloroindate and chlorotrimethylindate.

Dissolving a solid reactant in an organic solvent to provide aliquid-phase reactant allows such solid reactant to be used in thepresent process. In addition, using an organic solvent allows for thepreparation of organometallic compounds according to the present processthat might be solid under the conditions of the reactor, and reducesprecipitation in the reactor. For example, trimethyl indium, which canbe prepared according to the present process, melts at 88° C. anddecomposes explosively at 101-103° C. Using an organic solvent in thepreparation of trimethyl indium allows for reactor temperatures belowits melting point. In addition, trimethyl indium is known to be stablein solution, such as in squalane, at temperatures >125° C. for prolongedperiods. Using a solvent such as squalane when preparing trimethylindium allows for a greater range of reactor temperatures to be employedwithout decomposing the trimethyl indium.

Any metal-containing compound that can be reacted with a second reactantin a fluid can be used as the first reactant. As used herein, the term“metal” includes “metalloids.” The term “metalloid” as used hereinrefers to boron (Group 13), germanium (Group 14), phosphorus (Group 15),antimony (Group 15) and arsenic (Group 15). Suitable metal-containingfirst reactants contain at least one metal atom chosen from Group2-Group 15, preferably from Group 3 to Group 15, and more preferablyfrom Group 4 to Group 15. As used herein, Group 14 metals do not includecarbon and silicon and Group 15 metals do not include nitrogen.Particularly preferred metals are those in Groups 3, 4, 5, 8, 9, 10, 11,12, 13 and 15, even more preferably Groups 4, 5, 8, 11, 12, 13 and 15,and yet more preferably Groups 5, 12, 13 and 15. Exemplary metal atomsinclude, without limitation, magnesium, calcium, strontium, scandium,yttrium, lutetium, lawrencium, lanthanum, titanium, zirconium, hafnium,cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten,manganese, ruthenium, cobalt, rhodium, iridium, nickel, platinum,palladium, copper, silver, gold, zinc, cadmium, aluminum, gallium,indium, silicon, germanium, tin, phosphorus, antimony and antimony.Preferred metal atoms include magnesium, strontium, scandium, yttrium,lutetium, lawrencium, titanium, zirconium, hafnium, vanadium, niobium,tantalum, molybdenum, tungsten, manganese, ruthenium, cobalt, iridium,nickel, platinum, palladium, copper, silver, gold, zinc, cadmium,aluminum, gallium, indium, germanium, antimony and arsenic. It is morepreferred that the metal atom is magnesium, scandium, yttrium, lutetium,lawrencium, titanium, zirconium, hafnium, niobium, tantalum, molybdenum,tungsten, ruthenium, cobalt, iridium, nickel, platinum, palladium,copper, silver, gold, zinc, cadmium, aluminum, gallium, indium,germanium, antimony and arsenic, and even more preferred are magnesium,zirconium, hafnium, niobium, tantalum, molybdenum, tungsten, ruthenium,cobalt, iridium, nickel, copper, zinc, cadmium, aluminum, gallium,indium, germanium, antimony and arsenic, and yet more preferred aremagnesium, zirconium, hafnium, zinc, cadmium, aluminum, gallium, indium,germanium, antimony and arsenic. Particularly preferred metals arezirconium, hafnium, zinc, cadmium, aluminum, gallium, indium, antimonyand arsenic.

Preferred metal-containing compounds useful as the first reactant arethe halide, (C₁-C₄)carboxylate, amino and hydrocarbyl-containingcompounds of a metal atom chosen from Group 2-Group 15. Such preferredmetal-containing compounds have the general formula (I)

R_(a)Y_(b)M^(m)L  Formula (I)

wherein each R is independently chosen from ═H or a (C₁-C₁₀)hydrocarbylgroup; each Y is independently chosen from halide, (C₁-C₄)carboxylate,(C₁-C₅)alkoxy, R¹R²N or a diamino- or tri-amino group; M=Group 2-Group15 metal; R¹ and R² are independently chosen from H or (C₁-C₆)alkyl; L=aneutral ligand; m=the valence of M; a=0 to m; b=0 to m; and a+b=m. Itwill by those skilled in the art that a and b cannot both=0. The term“hydrocarbyl” refers to any hydrocarbon group, and includes alkyl groupsand aryl groups. Such hydrocarbyl group may optionally contain atomsother than carbon and hydrogen, such as oxygen or nitrogen. Preferredhydrocarbyl groups are methyl, ethyl, n-propyl, iso-propyl, n-butyl,sec-butyl, iso-butyl, tert-butyl, n-pentyl, neo-pentyl, cyclopentyl,hexyl, cyclohexyl, cyclopentadienyl, methylcyclopentadienyl,pentamethylcyclopentadienyl, (C₁-C₃)alkoxy(C₂-C₆)alkyl, amidinato,formamidinato, and β-diketonato. When the first reactant contains ahydrocarbyl group, such group is attached to the metal by way of ametal-carbon bond. Exemplary diamino- and tri-amino-groups for Yinclude, without limitation, 1,2-diaminoethyl,1,2-di-(N-methylamino)ethyl, 1,3-diaminopropyl,1,3-di-(N-methylamino)propyl, 1,2-diaminopropyl, and diethylenetriamineY is preferably chlorine, bromine, acetoxy, methoxy, ethyoxy, propoxy,butoxy, pentoxy, amino, methylamino, dimethylamino, ethylmethylamino,diethylamino, 1,2-diaminoethyl, 1,2-di-(N-methylamino)ethyl,1,3-diaminopropyl, and 1,3-di-(N-methylamino)propyl. It is morepreferred that Y is chlorine, bromine, acetoxy, methoxy, ethyoxy,propoxy, butoxy, pentoxy, amino, methylamino, dimethylamino,ethylmethylamino, and diethylamino.

Neutral ligands (L) may be optional in the metal-containing reactants.Such neutral ligands do not bear an overall charge and may function asstabilizers. Neutral ligands include, without limitation, CO, NO,nitrogen (N₂), amines, phosphines, alkylnitriles, alkenes, alkynes, andaromatic compounds. The term “alkene” includes any aliphatic compoundhaving one or more carbon-carbon double bonds. Exemplary neutral ligandsinclude, but are not limited to: (C₂-C₁₀)alkenes such as ethene,propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene,norbornene, vinylamine, allylamine, vinyltri(C₁-C₆)alkylsilane,divinyldi(C₁-C₆)alkylsilane, vinyltri(C₁-C₆)alkoxysilane anddivinyldi(C₁-C₆)alkoxysilane; (C₄-C₁₂)dienes such as butadiene,cyclopentadiene, isoprene, hexadiene, octadiene, cyclooctadiene,norbornadiene and α-terpinene; (C₆-C₁₆)trienes; (C₂-C₁₀)alkynes such asacetylene and propyne; and aromatic compounds such as benzene, o-xylene,m-xylene, p-xylene, toluene, o-cymene, m-cymene, p-cymene, pyridine,furan and thiophene. The number of neutral ligands depends upon theparticular metal chosen for M. When two or more neutral ligands arepresent, such ligands may be the same or different.

It is further preferred that the first reactant has the formula (II) R³_(c)Y¹ _(d)M²L_(n) wherein each R³ is chosen from H or (C₁-C₄)alkyl;each Y¹ is chosen from halide; M² is a Group 13 metal; L is as definedabove; c=0-3; d=0-3; c+d=3; and n=0-1. R³ is preferably H, methyl orethyl. Y¹ is preferably chlorine or bromine. In formula II, when L ispresent, it is preferred that the neutral ligand is a tertiary amine ortertiary phosphine. It is preferred that M² is indium or gallium.Preferred tertiary amines and tertiary phosphines aretri(C₁-C₄)alkylamines and tri(C₁-C₄)alkylphosphines.

Suitable second reactants may be any of the above describedmetal-containing compounds useful as the first reactant. Other compoundsuseful as the second reactant include, without limitation, compoundssuitable for alkylating the first reactant or acting as a ligand for themetal atom in the first reactant. In addition to the metal-containingcompounds of formula I, other preferred compounds useful as the secondreactant are: alkylamines; alkylphosphines; alkali metal or alkalineearth metal salts of β-diketonates, amidinates, formamidinates,guanidinates, and cyclopentadienyls; (C₁-C₄)alkoxides; (C₁-C₆)alkyllithium compounds; and (C₁-C₆)alkyl Grignard reagents. Suitablealkylamines are mono-, di-, and tri-(C₁-C₆)alkylamines, preferablymono-, di-, and tri-(C₁-C₄)alkylamines, and more preferablytri-(C₁-C₄)alkylamines. Particularly preferred alkylamines aretrimethylamine, triethylamine, and tripropylamine. Suitablealkylphosphines are mono-, di-, and tri-(C₁-C₆)alkylphosphines,preferably mono-, di-, and tri-(C₁-C₄)alkylphosphines, and morepreferably tri-(C₁-C₄)alkylphosphines. Particularly preferredalkylphosphines are trimethylphosphine, triethylpgosphine, andtripropylphosphine. The salts of β-diketonates, amidinates,formamidinates, guanidinates, and cyclopentadienyls are easily preparedby reacting the corresponding β-diketone, amidinine, formamidine,guanidine or cyclopentadiene with a suitable base, such as sodiumhydride. It is preferred that such salts are alkali metal salts.Suitable amidines and formamidines are those disclosed in U.S. Pat. No.2006/0141155 and U.S. Pat. No. 2008/0305260. Preferred cyclopentadienesare cyclopentadiene, methylcyclopentadiene andpentamethylcyclopentadiene. It will be appreciated by those skilled inthe art that the first reactant and the second reactant are different.

It is preferred that the second reactant is chosen from alkylamines,alkylphosphines and compounds of formula (II) described above. It isfurther preferred that the second reactant is chosen fromtri(C₁-C₄)alkylamines, tri(C₁-C₄)alkylphosphines and compounds offormula (II) described above, wherein M² is chosen from indium andgallium, and wherein Y¹ is chosen from chlorine and bromine.

The first reactant and the second reactant, either of these reactantsoptionally being in an organic solvent, are conveyed into the contactingzone of the reactor unit and subjected to conditions which providecontrolled mixing of the reactants in the one or more mixing zones.Controlling mixing of the reactants allows for more precise control ofthe overall reaction leading to the organometallic compound. Mixing iscontrolled in the present process by controlling the flows of thereactants in the laminar regime in the contacting zone and by the degreeof mixing in the mixing zone. The reactants are introduced into thecontacting zone of the reactor in a manner so as to have cocurrent andsubstantially laminar flow. By “substantially laminar,” it is meant thatthe flow of each reactant stream entering the mixing zone has a Reynoldsnumber (“Re”) of ≦2100, preferably ≦2000, more preferably ≦1500, andmost preferably ≦1000. It is further preferred that the flows of thefirst reactant stream and the second reactant stream are concentric.When the reactant streams have concentric flows, it is preferred thatthe center reactant stream has a lower Re than the outer reactantstream. The first reactant and second reactant can react at theinterface of the reactant streams in the contacting zone. This providesfor a very controlled rate of reaction to for the organometalliccompound, particularly for exothermic reactions. The reactant streamsthen enter the mixing zone where a greater degree of mixing is achieved,with a consequent increase in the rate of reaction, particularly forexothermic reactions. Control of the degree of mixing of the reactantsallows for the production of organometallic compounds in higher overallyields with reduced amounts of reaction by-products.

Once the first and second reactants are mixed, the resulting reactionmixture stream is subjected to conditions sufficient to allow thereactants to react to form the desired organometallic compound. Suchconditions are well known to those skilled in the art, and may includeheating, cooling, or a combination thereof. For exothermic reactions,the heat transfer zone of the reactor unit will contain a cooling unitin order to control the rate of reaction. For endothermic reactions, theheat transfer zone will contain a heating unit. Reaction time iscontrolled by controlling the residence time of the reactants in thereactor unit.

Following the reaction, the reaction mixture stream, which now includesthe organometallic compound produced, any unreacted first and secondreactants, reaction byproducts, and any organic solvent used, exits thereactor unit through the outlet in the heat transfer zone. Typically,the organometallic compound is obtained in a yield of ≧70% prior to anypurification steps. Preferably, the organometallic compound is obtainedin ≧90% yield, more preferably ≧95%, still more preferably ≧97%, andeven more preferably ≧98%.

The organometallic compound produced, unreacted first and secondreactants, reaction byproducts, and any organic solvent are conveyedfrom the outlet of the reactor unit to a separation unit. Suchseparation unit may employ any conventional technique for purificationof the organometallic compound, including, for example, crystallization,distillation or sublimation. Such separation techniques are well-knownin the art. Preferably, the organometallic compound is obtained in apurity of ≧95%, more preferably ≧97%, still more preferably ≧98%, yetmore preferably ≧99%, even more preferably ≧99.99%, and most preferably≧99.9999%.

The present continuous process is suitable to prepare a wide range oforganometallic compounds. Preferred organometallic compounds are thoseof the formula R⁴ _(e)M^(m)X_(m-e)L¹ (formula III), where each R⁴ isindependently (C₁-C₂₀)alkyl, (C₂-C₂₀)alkenyl, (C₂-C₂₀)alkynyl,(C₅-C₂₀)aryl, (C₅-C₂₀)aryl(C₁-C₁₀)alkyl, (C₁-C₂₀)alkoxy,(C₂-C₁₀)carbalkoxy, amino, (C₁-C₁₂)alkylamino(C₁-C₁₂)alkyl,di(C₁-C₂₀)alkylamino(C₁-C₁₂)alkyl, phosphino, and a divalent ligand;each X is independently H, R⁴, cyano, and halogen; L¹=a neutral ligand;e=the valence of the R⁴ group and is an integer ≧1; and m=the valence ofM. The “amino” groups include —NH₂, (C₁-C₁₂)alkylamino, anddi(C₁-C₁₂)alkylamino. Preferably, the amino groups are —NH₂,(C₁-C₆)alkylamino, and di(C₁-C₆)alkylamino, and more preferably —NH₂,(C₁-C₄)alkylamino, and di(C₁-C₄)alkylamino. “Phosphino” groups include—PH₂, (C₁-C₁₂)alkylphosphino, and di(C₁-C₁₂)alkylphosphino, preferablyinclude —PH₂, (C₁-C₆)alkylphosphino, and di(C₁-C₆)alkylphosphino, andmore preferably include —PH₂, (C₁-C₄)alkylphosphino, anddi(C₁-C₄)alkylphosphino. The above R⁴ groups may optionally besubstituted by replacing one or more hydrogen atoms with one or moresubstituent groups, such as halogen, carbonyl, hydroxyl, cyano, amino,alkylamino, dialkylamino, and alkoxy. For example, when R⁴ is a(C₁-C₂₀)alkyl group, such group may contain a carbonyl within the alkylchain. Suitable divalent ligands include, without limitation,β-diketonates, amidinates, formamidinates, phosphoamidinates,guanidinates, β-diketiminates, bicyclic amidinates and bicyclicguanidinates. Preferred divalent ligands include β-diketonates,amidinates, formamidinates, phosphoamidinates, and guanidinates.Depending on the particular metal atom, the organometallic compounds offormula III may optionally contain one or more neutral ligands (L). Suchneutral ligands do not bear an overall charge. Neutral ligands include,without limitation, CO, NO, nitrogen, amines, ethers, phosphines,alkylphosphines, arylphosphines, nitriles, alkenes, dienes, trienes,alkynes, and aromatic compounds. Adducts of organometallic compounds offormula III with amines or phosphines, such as tertiary amines ortertiary phosphines, are contemplated by the present invention.

Preferably, each R⁴ group in formula III is independently selected from(C₁-C₁₀)alkyl, (C₂-C₁₀)alkenyl, (C₂-C₁₀)alkynyl, (C₅-C₁₅)aryl,(C₅-C₁₀)aryl(C₁-C₆)alkyl, (C₁-C₁₀)alkoxy, (C₂-C₁₀)carbalkoxy, amino,(C₁-C₆)alkylamino(C₁-C₆)alkyl, di(C₁-C₆)alkylamino(C₁-C₆)alkyl,phosphino, and a divalent ligand; and more preferably (C₁-C₆)alkyl,(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, (C₅-C₁₀)aryl, (C₅-C₈)aryl(C₁-C₆)alkyl,(C₁-C₆)alkoxy, (C₂-C₆)carbalkoxy, amino, (C₁-C₄)alkylamino(C₁-C₆)alkyl,di(C₁-C₄)alkylamino(C₁-C₆)alkyl, phosphino, and a divalent ligand. It isfurther preferred that each R⁴ is independently selected from(C₁-C₅)alkyl, (C₂-C₃)alkenyl, (C₂-C₃)alkynyl, (C₅-C₈)aryl,(C₅-C₈)aryl(C₁-C₄)alkyl, (C₁-C₅)alkoxy, (C₂-C₅)carbalkoxy, amino,(C₁-C₄)alkylamino(C₁-C₄)alkyl, di(C₁-C₄)alkylamino(C₁-C₄)alkyl,phosphino, and a divalent ligand, and still more preferably(C₁-C₄)alkyl, (C₂-C₃)alkenyl, (C₅-C₈)aryl, (C₁-C₅)alkoxy, amino,(C₁-C₃)alkylamino(C₁-C₄)alkyl, di(C₁-C₃)alkylamino(C₁-C₄)alkyl,phosphino, and a divalent ligand.

Preferred organometallic compounds have the structure of formula (IV)

R⁵ _(x)X² _(p-x)M^(3p)  Formula (IV)

wherein each R⁵ is independently chosen from (C₁-C₆)alkyl,(C₂-C₆)alkenyl, (C₁-C₄)alkylamino(C₁-C₆)alkyl,di(C₁-C₄)alkylamino(C₁-C₆)alkyl, (C₅-C₁₀)aryl, —NH₂, (C₁-C₄)alkylamino,and di(C₁-C₄)alkylamino; each X² is independently chosen from H,halogen, (C₁-C₁₀)alkoxy and R⁵; M³ is a Group 2, 4 or 13 metal; x is thevalence of the R⁵ group and is an integer; p is the valence of M³; and1≦x≦p. Adducts of organometallic compounds of formula II with amines orphosphines, such as tertiary amines or tertiary phosphines, arecontemplated by the present invention. It is preferred that each R⁵ isindependently chosen from (C₁-C₄)alkyl, (C₂-C₄)alkenyl, (C₅-C₁₀)aryl,—NH₂, (C₁-C₄)alkylamino, and di(C₁-C₄)alkylamino; and more preferably(C₁-C₄)alkyl, (C₅-C₈)aryl, —NH₂, (C₁-C₄)alkylamino, anddi(C₁-C₄)alkylamino. Exemplary groups for R1 include, withoutlimitation, methyl, ethyl, n-propyl, iso-propyl, butyl, tert-butyl,iso-butyl, sec-butyl, n-pentyl, iso-pentyl, neo-pentyl, vinyl, allyl,propargyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminopropyl,phenyl, cyclopentadienyl, methylcyclopentadienyl,pentamethylcyclopentadienyl, methylamino, dimethylamino, andethylmethylamino. When X² is a halogen, chlorine and bromine arepreferred and chlorine is more preferred. When M³ is a Group 2 metal,x=1 or 2. When M³ is a Group 4 metal, x=1, 2, 3 or 4. When M³=a Group 13metal, x=1, 2 or 3. M³ is preferably magnesium, zirconium, hafnium,aluminum, indium or gallium, and more preferably aluminum, indium orgallium.

Exemplary organometallic compounds include, but are not limited to:trialkyl indium compounds such as trimethyl indium, triethyl indium,tri-n-propyl indium, tri-iso-propyl indium, dimethyl iso-propyl indium,dimethyl ethyl indium, dimethyl tert-butyl indium, methyl di-tert-butylindium, methyl di-isopropyl indium, and tri-tertiarybutyl indium;trialkyl indium-amine adducts; dialkyl haloindium compounds such asdimethyl indium chloride; alkyl dihaloindium compounds such as methyldichloroindium; cyclopentadienyl indium; trialkylindium-trialkyl-phosphine adducts such as trimethyl indium-trimethylphosphine adduct; trialkyl gallium compounds such as trimethyl gallium,triethyl gallium, tri-iso-propyl gallium, tri-tert-butyl gallium,dimethyl iso-propyl gallium, diethyl tert-butyl gallium, methyldi-iso-propyl gallium, dimethyl tert-butyl gallium, dimethyl neo-pentylgallium, and methyl ethyl iso-propyl gallium; trialkyl gallium-amineadducts; trialkyl gallium-phosphine adducts; alkyl dihalogalliumcompounds such as methyl dichlorogallium, ethyl dichlorogallium andmethyl dibromogallium; dialkyl halogallium compounds such as dimethylgallium chloride and diethyl gallium chloride; trialkylaluminumcompounds such as trimethyl aluminum, triethyl aluminum, tri-n-propylaluminum, tri-iso-propyl aluminum, tri-tert-butyl aluminum, dimethyliso-propyl aluminum, dimethyl ethyl aluminum, dimethyl tert-butylaluminum, methyl di-tert-butyl aluminum, and methyl di-iso-propylaluminum; diaklyl haloaluminum compounds such as dimethyl aluminumchloride and diethylaluminum chloride; alkyl dihaloaluminum compoundssuch as methyl aluminum dichloride, ethyl aluminum dichloride, and ethylaluminum dibromide; metal dialkylamido compounds such astetrakis(ethylmethylamino) zirconium and tetrakis(ethylmethylamino)hafnium; metal beta-diketonates such as beta-diketonates of hafnium,zirconium, tantalum and titanium; and metal amidinates such asamidinates of copper, lanthanum, ruthenium, and cobalt. For example,Group 13 organometallic compounds may be prepared using the reactantsdescribed in, for example, U.S. Pat. Nos. 5,756,786; 6,680,397; and6,770,769. Metal amidinate compounds may be prepared using the reactantsdescribed in, for example, U.S. Pat. Nos. 7,638,645; and 7,816,550.

The organometallic compounds prepared by the present process may be usedin a variety of applications that demand the use of high purityorganometallic compounds, such as in certain catalyst applications andin the manufacture of electronic devices such as light emitting diodes.The present organometallic compounds may also be used as intermediatesin the preparation of other organometallic compounds.

EXAMPLE 1

The following table illustrates various organometallic compounds to beproduced according to the present process. Suitable organic solvents arelisted where such solvents are needed or may be optionally used.

First Reac- Compound tant Second Reactant Solvent TDMAHf HfCl₄ (CH₃)₂NLiMesitylene or durene TDMAZr ZrCl₄ (CH₃)₂NLi Mesitylene or durene TEMAHfHfCl₄ (CH₃)(CH₃CH₂)NLi Mesitylene or durene TEMAZr ZrCl₄(CH₃)(CH₃CH₂)NLi Mesitylene or durene (CH₃)₂InCl InCl₃ (CH₃)₃Al Squalaneor mesitylene (CH₃)₃Ga GaCl₃ (CH₃)₃Al Toluene or mesitylene (CH₃)₃InInCl₃ (CH₃)₃Al Squalane or mesitylene (CH₃CH₂)₃Ga GaCl₃ (CH₃CH₂)₃AlToluene or LAB (CH₃CH₂)₃In InCl₃ (CH₃CH₂)₃Al Squalane or mesitylene(CH₃CH₂)₂GaCl GaCl₃ (CH₃CH₂)₃Al Toluene or LABThe abbreviations have the following meanings: LAB=linear alkylbenzenes; TDMA=tetrakis(dimethylamino) or [(CH₃)₂N]₄; andTEMA=tetrakis(ethylmethylamino) or [(CH₃)(CH₃CH₂)N]₄.

EXAMPLE 2

To a reactor having a contacting zone having first and second inlets,multiple heat transfer zones, a plurality of mixing zones havingdifferent radii of curvature, and a reaction zone following each mixingzone was fed a predominantly liquid stream of TMA at 200-300 kPa as afirst reactant at a temperature of 10-30° C. at a flow rate of 10-20units/hr and a predominantly liquid stream of tripropylamine (“TPA”) asa second reactant also at 200-300 kPa and a temperature of 10-30° C. ata flow rate of 20-40 units/hour into a laminar environment of a reactorinlet. The flow rates were set to control a molar excess of TPA atslightly more than 1/1 to TMA. Both reactant streams were delivered tothe mixing zone of the reactor having concentric and substantiallylaminar flows. The Reynolds number for each reactant stream entering themixing zone was ≦1000. The reactant streams had a total residence timein the reactor of >20 seconds. Upon exiting the reactor, the product(TMA-TPA adduct) stream was conveyed to a separation unit to removeimpurities. This reaction was operated mostly continuously for more than24 hours with only a few short interruptions resulting in a productionof >450 kg of material.

EXAMPLE 3

To a reactor similar to that used in Example 2, was fed a predominantlyliquid stream of TMA-TPA adduct from Example 2 as a first reactant at apressure of 200-300 kPa, a temperature of 40-60° C. and at a flow rateof 20-40 units/hr and a predominantly liquid stream of gallium chloridein a aromatic hydrocarbon solvent as a second reactant at a temperatureof 2-10° C. and a pressure of 200-300 kPa and at a flow rate of 20-40units/hr to maintain a molar ratio of aluminum to gallium metal atgreater than 1/1. The heat transfer zone of the reactor maintained thereactor outlet temperature of 85-100° C. The reactor was operatedcontinuously for more than 24 hours and during this time the product(trimethylgallium or “TMG”) was continuously purified in a separationunit producing more than 100 kg of high purity TMG at an overall yieldof >85%.

EXAMPLE 4

The procedure of Example 3 was repeated and the overall yield afterpurification was >90%.

EXAMPLE 5

The procedure of Example 2 is repeated except that triethylaluminum isused as the first reactant to produce triethylaluminum-TPA adduct.

EXAMPLE 6

The procedure of Example 3 is repeated except that thetriethylaluminum-TPA adduct from Example 5 is used as the first reactantto produced triethylgallium.

EXAMPLE 7

The procedure of Example 3 is repeated except that lithium dimethylamidein mesitylene is used as the first reactant and hafnium tetrachloride inmesitylene is used as the second reactant to producetetrakis(dimethylamino) hafnium.

EXAMPLE 8

The procedure of Example 7 is repeated except that hafnium tetrachlorideis replaced with zirconium tetrachloride to producetetrakis(dimethylamino) hafnium.

EXAMPLE 9

The procedure of Example 7 is repeated except that lithiumethylmethylamide in mesitylene is used as the first reactant to producetetrakis(ethylmethylamino) hafnium.

What is claimed is:
 1. An apparatus for continuously manufacturing anorganometallic compound comprising: (a) a source of a first reactantstream wherein the first reactant comprises a metal; (b) a source of asecond reactant stream; (c) a laminar flow contacting zone forcocurrently contacting the first reactant stream and the second reactantstream; (d) a mixing zone comprising a turbulence-promoting device; and(e) a heat transfer zone.
 2. The apparatus of claim 1 wherein theturbulence-promoting device is chosen from bends, spirals, venturis,wavy-walled columns, orifices and static mixers.
 3. The apparatus ofclaim 2 wherein the turbulence-promoting device is chosen from venturis,bends, wavy-walled reactors and combinations thereof.
 4. The apparatusof claim 1 further comprising a plurality of turbulence-promotingdevices.
 5. The apparatus of claim 4 wherein the plurality ofturbulence-promoting devices comprises at least 2 different mixingzones.
 6. The apparatus of 1 further comprising a plurality of mixingzones with turbulence-promoting devices.
 7. The apparatus of claim 1further comprising a reaction zone following the mixing zone.